EP2787027A1 - Film de polyester, feuille arrière de cellule solaire et cellule solaire - Google Patents
Film de polyester, feuille arrière de cellule solaire et cellule solaire Download PDFInfo
- Publication number
- EP2787027A1 EP2787027A1 EP12852635.7A EP12852635A EP2787027A1 EP 2787027 A1 EP2787027 A1 EP 2787027A1 EP 12852635 A EP12852635 A EP 12852635A EP 2787027 A1 EP2787027 A1 EP 2787027A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pet
- film
- polyester
- comparative example
- solar cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 91
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 229920000728 polyester Polymers 0.000 claims description 58
- 239000002245 particle Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 description 167
- 239000005020 polyethylene terephthalate Substances 0.000 description 167
- 230000000052 comparative effect Effects 0.000 description 123
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 101
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 69
- 229910052710 silicon Inorganic materials 0.000 description 69
- 239000010703 silicon Substances 0.000 description 69
- 239000000377 silicon dioxide Substances 0.000 description 50
- 239000010410 layer Substances 0.000 description 22
- -1 solar cells Substances 0.000 description 19
- 239000008188 pellet Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002987 primer (paints) Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 2
- FAIFRACTBXWXGY-JTTXIWGLSA-N COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 Chemical compound COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 FAIFRACTBXWXGY-JTTXIWGLSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229960002479 isosorbide Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical class CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- XFEGRFIENDJTCK-UHFFFAOYSA-N 2-phenyl-2,3-dihydroindene-1,1-dicarboxylic acid Chemical compound C1C2=CC=CC=C2C(C(=O)O)(C(O)=O)C1C1=CC=CC=C1 XFEGRFIENDJTCK-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- LBVBDLCCWCJXFA-UHFFFAOYSA-N adamantane-1,2-dicarboxylic acid Chemical compound C1C(C2)CC3CC1C(C(=O)O)C2(C(O)=O)C3 LBVBDLCCWCJXFA-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
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- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- AJDJKHROQJQURF-UHFFFAOYSA-N phenanthrene-1,2-dicarboxylic acid Chemical compound C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1 AJDJKHROQJQURF-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/24405—Polymer or resin [e.g., natural or synthetic rubber, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/24413—Metal or metal compound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
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- Y10T428/24372—Particulate matter
- Y10T428/24421—Silicon containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/24372—Particulate matter
- Y10T428/24421—Silicon containing
- Y10T428/2443—Sand, clay, or crushed rock or slate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to a polyester film having excellent durability.
- the present invention also relates to a solar cell backsheet and solar cell which comprise the polyester film.
- Polyester films have been used in various applications, such as materials of magnetic recording media, electrical insulators, solar cells, capacitors and packagings and industrial materials, by taking advantage of their characteristics such as excellent mechanical, thermal and surface properties as well as excellent heat resistance.
- polyester films have been used as a member constituting a solar cell backsheet (Patent Documents 1 and 2).
- Patent Documents 1 and 2 the demand for solar cells that generate clean energy as semi-permanent and pollution-free next-generation energy source has increased, and polyester films have been used as a member constituting a solar cell backsheet.
- Patent Documents 1 and 2 As a way of extending the service live of solar cells, there is an increasing demand for an improvement in the wet heat resistance and partial discharge voltage of solar cell backsheets and polyester films used therein (Patent Documents 1 and 2).
- films to be used in mold-releasing applications films having controlled height and number of productions (peaks) on the surface have been proposed (Patent Documents 3 and 4).
- Patent Document 1 a polyester film having excellent wet heat resistance is proposed; however, even when this polyester film is used, the service life of a solar cell backsheet and that of a solar cell are not extended so much.
- the present inventors investigated the cause thereof and, as a result, it was revealed that the moisture resistance of a polyester film is reduced for some reason when the polyester film is incorporated into a solar cell backsheet or solar cell.
- Patent Documents 3 and 4 are used in mold-releasing applications. Further, the technologies of Patent Documents 3 and 4 focus on projections of very low in height among those projections existing on the film surface and specify the number of such projections. Thus, even when the films of Patent Documents 3 and 4 are incorporated in a solar cell backsheet, the wet heat resistance of the resulting solar cell backsheet is very poor.
- an object of the present invention is to provide a polyester film whose wet heat resistance is not reduced even when incorporated into a solar cell backsheet or solar cell.
- the present invention is characterized by the following (1) to (7).
- a polyester film having excellent wet heat resistance can be provided.
- Polyester used in the present invention is obtained by polycondensation of a dicarboxylic acid component and a diol component. It is noted here that the term “component” used herein refers to the smallest unit that can be obtained by hydrolysis of polyester.
- dicarboxylic acid component constituting the polyester examples include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosanedioic acid, pimelic acid, azelaic acid, methylmalonic acid and ethylmalonic acid; alicyclic dicarboxylic acids such as adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexane dicarboxylic acid and decalin dicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic
- examples of the diol component constituting the polyester include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol and 1,3-butanediol; alicyclic diols such as cyclohexane dimethanol, spiroglycol and isosorbide; aromatic diols such as bisphenol A, 1,3-benzene dimethanol, 1,4-benzene dimethanol and 9,9'-bis(4-hydroxyphenyl)fluorene; and a series of a plurality of these diols.
- aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol and 1,3-butanediol
- alicyclic diols such
- the polyester may be copolymerized with a monofunctional compound such as lauryl alcohol or phenyl isocyanate and the polyester may also be copolymerized with, for example, a trifunctional compound such as trimellitic acid, pyromellitic acid, glycerol, pentaerythritol or 2,4-dioxybenzoic acid, as long as the resulting polymer is substantially linear without being excessively branched or cross-linked.
- a monofunctional compound such as lauryl alcohol or phenyl isocyanate
- a trifunctional compound such as trimellitic acid, pyromellitic acid, glycerol, pentaerythritol or 2,4-dioxybenzoic acid
- the polyester may be further copolymerized with a small amount of an aromatic hydroxycarboxylic acid such as p-hydroxybenzoic acid, m-hydroxybenzoic acid or 2,6-hydroxynaphthoic acid, p-aminophenol or p-aminobenzoic acid, as long as the effects of the present invention are not adversely affected.
- an aromatic hydroxycarboxylic acid such as p-hydroxybenzoic acid, m-hydroxybenzoic acid or 2,6-hydroxynaphthoic acid, p-aminophenol or p-aminobenzoic acid, as long as the effects of the present invention are not adversely affected.
- the polyester polyethylene terephthalate and polyethylene naphthalate are preferably used.
- the polyester may be a copolymer or denaturation product thereof. From the standpoint of crystallinity, it is preferred that the polyester comprise polyethylene terephthalate and/or polyethylene naphthalate as main component(s).
- polyethylene terephthalate and/or polyethylene naphthalate as main component(s) means that not less than 85 mol% of all repeating units of the polyester is ethylene terephthalate and/or ethylene naphthalate. It is particularly preferred that 90 mol% or more of all repeating units of the polyester be ethylene terephthalate and/or ethylene naphthalate.
- the polyester film of the present invention is required to have a peak count SPc_L (400 nm) of not less than 100 and a peak count SPc_H (4,000 nm) of not more than 10 on at least one surface.
- the polyester film When the polyester film is incorporated into a solar cell backsheet as well as during transfer and production of a solar cell, the polyester film repeatedly comes in contact with other members. Such contact between the polyester film and other members damages the surface of the polyester film, allowing water to infiltrate into the film therethrough. It is believed that hydrolysis of the polyester film is consequently facilitated and the wet heat resistance of the polyester film is thereby reduced. Particularly, a metal is used in the frames and the like of solar cells and metals are generally harder than polyester. Therefore, it is speculated that, when the polyester film is used in a solar cell application, the surface of the polyester film is very likely to be damaged.
- the SPc_L 400 nm
- the SPc_L (400 nm) is more preferably not less than 150, still more preferably not less than 250.
- the SPc_H (4,000 nm) is more than 10, a reduction in durability caused by such damage can be inhibited; however, since the surface area is increased, water is likely to infiltrate into the polyester film and this leads to a problem of deterioration in the wet heat resistance.
- the SPc_H (4,000 nm) is more preferably 5 or less, still more preferably 2 or less, particularly preferably 1 or less. Further, the SPc_L (400 nm) is preferably 500 or less since good durability is attained.
- the SPc_L (400 nm) and SPc_H (4,000 nm) can be controlled by adjusting the size and concentration of particles to be added as well as the domain size and concentration of a resin to be added.
- the amount of terminal carboxyl groups is required to be 0 to 25 eq/ton.
- the polyester film is likely to be hydrolyzed due to autocatalytic actions of terminal carboxyl groups, and this leads to a problem of reduction in the wet heat resistance.
- the upper limit of the amount of terminal carboxyl groups is more preferably 20 eq/ton, still more preferably 16 eq/ton.
- the amount of terminal carboxyl groups is more preferably in the range of 0 to 20 eq/ton, still more preferably 0 to 16 eq/ton.
- the amount of terminal carboxyl groups can be controlled by adjusting, for example, the raw materials and melt-kneading method to be used.
- the polyester film of the present invention comprise, as the outermost layer, a layer containing particles of 2 ⁇ m or larger in size in an amount of 0.1 to 5% by mass.
- the particle size is smaller than 2 ⁇ m, surface projections are not likely to be formed, so that the polyester film may be easily damaged.
- the particle content is less than 0.1% by mass, since surface projections are not likely to be formed and this makes the polyester film more likely to be damaged, the durability may be reduced.
- the particle content is greater than 5% by mass, since surface projections are excessively formed and this leads to an increase in the surface area, the durability may be deteriorated.
- the lower limit of the particle content is more preferably 0.2% by mass, still more preferably 0.4% by mass.
- the upper limit of the particle content is more preferably 4% by mass, still more preferably 2% by mass.
- Examples of the particle type include inorganic particles and organic particles.
- examples of the inorganic particles include clay, mica, titanium oxide, calcium carbonate, kaolin, talc, wet-type silica, dry-type silica, colloidal silica, calcium phosphate, barium sulfate, alumina, zirconia and aluminosilicate particles.
- examples of the organic particles include those particles comprising an acrylic acid, a styrene resin, a thermosetting resin, silicone, an imide compound or the like as a constituent. Particles that are precipitated by a catalyst or the like added at the time of performing a polyester polymerization reaction (so-called internal particles) can also be preferably used.
- aluminosilicate particles are preferred because of their low hygroscopicity. Since those particles of low hygroscopicity retain only a small amount of water, even when a film is formed with an addition of such particles to a polyester, deterioration of the polyester caused by water is inhibited, so that the durability of the resulting film is likely to be improved.
- the surface roughness of the polyester film can be controlled.
- the film of the present invention comprises a polyester.
- the film of the present invention may also comprise a resin that is different from the polyester constituting the film.
- the film of the present invention may also comprise a resin that is not compatible with the polyester constituting the film (hereinafter, referred to as "incompatible resin").
- incompatible resin is preferably dispersed in the polyester. The reason for this is because it allows projections to be formed on the film surface.
- the incompatible resin contained in the film have a domain size of 500 to 3,000 nm. When the domain size is smaller than 500 nm, since surface projections are not likely to be formed and this makes the polyester film more likely to be damaged, the durability may be reduced. When the domain size is larger than 3,000 nm, surface projections are excessively formed, so that the durability of the film may be reduced.
- the type of the incompatible resin is not particularly restricted as long as it is different from the polyester constituting the film.
- the incompatible resin may be, for example, a polyester resin (which is, however, required to be of a different type from the polyester constituting the film), a styrene resin or a polyimide resin, and the incompatible resin is particularly preferably a polyester resin.
- a layer containing the incompatible resin be arranged as the outermost layer.
- the reason for this is because surface projections can be efficiently formed by arranging the layer containing an incompatible resin as the outermost layer. It is noted here that the domain size is controlled by adjusting the type and viscosity of the resin.
- the thickness of the polyester film can be determined in accordance with the intended use and, in a solar cell backsheet application, the thickness of the polyester film is preferably 25 to 250 ⁇ m.
- the thickness is less than 25 ⁇ m, there are problems in that, for example, the film does not have sufficient firmness and transportation thereof is thus difficult. Meanwhile, when the thickness is greater than 250 ⁇ m, the film is excessively thick and its processability may thus be poor.
- the lower limit of the thickness is more preferably 30 ⁇ m, still more preferably 40 ⁇ m.
- the upper limit of the thickness is more preferably 220 ⁇ m, still more preferably 200 ⁇ m.
- the thickness is more preferably in the range of 30 to 220 ⁇ m, still more preferably 40 to 200 ⁇ m.
- polyester film of the present invention is produced, for example, as described below.
- a polyester pellet is melted in an extruder, extruded from a mouthpiece, and then solidified by cooling to be molded into a sheet form.
- the polymer in order to remove unmelted materials from the polymer, the polymer may be filtered through a fiber-sintered stainless-metal filter.
- a variety of additives such as a compatibilizer, a plasticizer, an anti-weathering agent, an antioxidant, a heat stabilizer, a lubricant, an electrification inhibitor, a brightening agent, a coloring agent, a conductive agent, a flame retardant, a flame retardant aid, a pigment and a dye, may also be added.
- the sheet-form article obtained in the above-described manner is biaxially stretched in the machine and transverse directions and subsequently heat-treated.
- the mode of stretching encompasses sequential biaxial stretching in which, for example, stretching is performed in the machine direction and then in the transverse direction; simultaneous biaxial stretching in which stretching is performed in both the machine and transverse directions at the same time using a simultaneous biaxial tenter or the like; and a combination of sequential biaxial stretching and simultaneous biaxial stretching.
- PET polyethylene terephthalate
- the present invention is not restricted to a polyester film in which PET is used and that other polymer may be used as well.
- PET polyethylene terephthalate
- extrusion and stretching can be carried out at a temperature higher than the temperature described below.
- polyethylene terephthalate is prepared.
- This polyethylene terephthalate is produced by either of the following processes, that is, (1) a process in which a low-molecular-weight polyethylene terephthalate or oligomer is obtained by direct esterification reaction using terephthalic acid and ethylene glycol as raw materials and a polymer is then obtained by subsequent polycondensation reaction using antimony trioxide or the like as a catalyst; and (2) a process in which a low-molecular-weight product is obtained by transesterification reaction using dimethyl terephthalate and ethylene glycol as raw materials and a polymer is then obtained by subsequent polycondensation reaction using antimony trioxide or the like as a catalyst.
- the thus obtained PET pellet be heat-treated at a temperature of 220°C for at least 8 hours under a reduced pressure of 1 mmHg using a rotary vacuum polymerization apparatus so as to increase the intrinsic viscosity.
- a method in which a PET pellet (masterbatch) containing particles or a resin at a high concentration is prepared by directly mixing the particles or a resin with a PET pellet and kneading the particles or a resin into PET using a vented biaxial kneading extruder heated to 270 to 295°C is effective.
- the dried PET pellet is fed to an extruder heated to 265 to 280°C under nitrogen gas flow or under reduced pressure so that the intrinsic viscosity is not reduced.
- the PET pellet is then extruded from a slit T-die and cooled on a casting roll to obtain an unstretched film.
- two or more extruders and a manifold or joint block are used to melt and laminate a plurality of different polymers.
- an unstretched film is subjected to MD stretching.
- the longitudinal stretching machine comprises a preheating roll, a stretching roll and a cooling roll as well as a nip roll which reduces tension and inhibits film slippage.
- the film traveling on the stretching roll is pressed down and nipped by the stretch-nip roll with a constant pressure (nip pressure) to reduce tension and the film is stretched by the difference in peripheral speed between the stretching roll and the following cooling roll that are rotating.
- the stretching roll and the stretch-nip roll are rolls for pressing and nipping the film.
- the stretching roll and the stretch-nip roll be both silicon rolls having a surface hardness, which is measured by a durometer (type A) in accordance with JIS-K 6253 (2006), of 30° to 70°.
- a durometer type A
- the surface hardness is more preferably 30° to 45°.
- the surface hardness is less than 30°, tension may not be sufficiently reduced by the rolls and this may result in the occurrence of non-uniform stretching, which is not preferred.
- the nip pressure is preferably 0.05 to 0.2 Pa.
- the nip pressure is more preferably 0.05 to 0.15 MPa.
- the nip pressure is higher than 0.15 MPa, the projections are crushed and the film surface may thus become more likely to be damaged.
- the nip pressure is less than 0.05 MPa, tension may not be sufficiently reduced by the rolls and this may result in the occurrence of non-uniform stretching, which is not preferred.
- the MD stretching is performed at a temperature of (glass transition temperature (hereinafter, referred to as "Tg") + 10) to (Tg + 50)°C and a draw ratio of 1.2 to 5.0 times. After the stretching, the thus stretched film is cooled by a group of cooling rolls at 20 to 50°C.
- Tg glass transition temperature
- a stenter is an apparatus which laterally stretches a film by spreading the space between the clips holding each end of the film and is divided into a preheating zone, a stretching zone, a heat treatment zone and a cooling zone.
- the air flow rate in the preheating zone is preferably 1 to 20 m/s.
- the air flow rate in the preheating zone is higher than 20 m/s, the projecting parts of the surface are rapidly heated, so that the projections may be reduced in size.
- the number of projections on the film surface is also reduced; therefore, there is a problem that the film surface is likely to be damaged.
- the air flow rate in the preheating zone is more preferably 1 to 5 m/s.
- the air flow rate is measured at the nozzle outlet and the space between the nozzle and the film is preferably 120 mm.
- the TD stretching is performed at a draw ratio of 2.0 to 6.0 times and a temperature of (Tg) to (Tg + 50)°C.
- the resulting film is subjected to a heat fixation treatment.
- the film is heat-treated in a temperature range of 150 to 240°C while being extended or relaxed in the transverse direction.
- the heat treatment is performed for 0.5 to 10 seconds.
- the thus heat-treated film is cooled to 25°C in the cooling zone.
- the air flow rate in the cooling zone is preferably 3 to 30 m/s.
- the air flow rate in the cooling zone is more preferably 15 to 30 m/s.
- the air flow rate is lower than 15 m/s, it takes a long time for the film to be cooled and the surface projections are reduced in size, so that the film surface may be easily damaged.
- the air flow rate is higher than 30 m/s, the film is locally cooled and non-uniform cooling results in non-uniform physical properties; therefore, such an air flow rate is not preferred. Thereafter, by removing film edges, the polyester film of the present invention can be obtained.
- the surface morphology of a subject polyester film is measured in accordance with JIS B0601 (1994) under the following conditions.
- the SPc_L (400 nm) represents the number of projections of 400 nm or higher in the reference area and the SPc_H (4,000 nm) represents the number of projections of 4,000 nm or higher in the reference area. These values are determined by analyzing the projections using an analysis system.
- the amount of terminal carboxyl groups is measured for the entirety of a subject film by the method described by Maulice (Reference: M.J. Maulice, F. Huizinga, Anal. Chim. Acta, 22: 363 (1960 )).
- the surface of a subject film is etched with 1N potassium hydroxide in methanol solution to expose particles, and photographs of 100 viewing fields are taken under a scanning electron microscope (SEM) at a magnification of ⁇ 10,000.
- SEM scanning electron microscope
- the area of each particle on the thus taken photographs was measured using an image analyzer and the diameter of a circle having the same area as the measured area was calculated and defined as the equivalent circle diameter. For each particle, the diameter of equivalent circle was determined and defined as the size of the particle.
- the domain size of a resin in a film means the average length of the elliptical major axis of domain sizes measured on plural observation surfaces and it can be determined by the following measurement method.
- a cross-section of a subject film is observed under a transmission electron microscope at an accelerating voltage of 100 kV and a photograph thereof taken at a magnification of ⁇ 20,000 is scanned into an image analyzer. Then, 100 arbitrary dispersed phases (island parts) are selected and, as required, image processing is performed to determine their domain size as a number-average value. Specifically, this process is carried out as follows.
- a subject film was cut by an ultra-thin cutting method (a) in the direction parallel to the machine direction and perpendicular to the film surface, (b) in the direction parallel to the transverse direction and perpendicular to the film surface and (c) in the direction parallel to the film surface (that is, in the direction perpendicular to the film thickness direction), thereby preparing samples.
- the samples may be stained with osmic acid, ruthenium acid or the like.
- the cut surfaces are observed under a transmission electron microscope (model H-7100FA, manufactured by Hitachi Ltd.) at an accelerating voltage of 100 kV and photographs thereof are taken at a magnification of ⁇ 20,000. The thus obtained photographs were scanned into an image analyzer as images.
- La is determined as the number-average value of the maximum length measured for 100 arbitrary dispersed phases on the cut surface of (a);
- Lb is determined as the number-average value of the maximum length measured for 100 arbitrary dispersed phases on the cut surface of (b);
- Lc is determined as the number-average value of the maximum length measured for 100 arbitrary dispersed phases on the cut surface of (c).
- the value of (La + Lb + Lc)/3 was defined as the average domain size of the dispersed phases.
- samples were cut out in a size of 1 cm ⁇ 20 cm and stretched at a chuck distance of 5 cm and a tensile rate of 300 mm/min to measure the elongation at break.
- the film surface of 5 cm ⁇ 20 cm in size is rubbed 10 times with a sandpaper (#800) at a contact pressure of 0.01 MPa and the wet heat resistance is evaluated.
- the thus obtained measurement pieces are treated in a pressure cooker manufactured by Tabai ESPEC Corp. at a temperature of 125°C and a relative humidity of 100% RH, and the elongation at break is then measured in accordance with the above (6).
- the elongation at break E0 is measured in accordance with the above (6). From the thus obtained values of elongation at break, E0 and E1, the retention of elongation is calculated using the following equation (f) and the treatment time at which the retention of elongation is 50% is defined as half-life of elongation.
- the film durability was evaluated as follows.
- the evaluations of A to C are good and thereamong, A is the best evaluation.
- an adhesive prepared by mixing commercially-available polyester-based main adhesive LX703VL and polyisocyanate-based curing agent KR90 (both of which are manufactured by DIC Corporation) at a weight ratio of 15: 1 (dry weight: 4 g/m 2 ) was coated on the
- the durability of the thus obtained backsheet was evaluated in the same manner as in the above (7), except that the backsheet was not rubbed with sandpaper.
- the half-life of elongation was 65 hours or longer: A When the half-life of elongation was 55 hours to shorter than 65 hours: B When the half-life of elongation was 45 hours to shorter than 55 hours: C When the half-life of elongation was 35 hours to shorter than 45 hours: D When the half-life of elongation was shorter than 35 hours: E
- an ethylene-vinyl acetate copolymer resin (hereinafter, referred to as "EVA") sheet, a solar cell and a light-transmitting glass plate are laminated and integrated by heat-pressing to form a solar cell module.
- EVA ethylene-vinyl acetate copolymer resin
- the thus obtained solar cell module is taken out and fed to the panel loading step of a solar cell panel production line.
- the primer coating step the surface to be adhered with an aluminum frame is coated with a primer.
- the resulting solar cell module is exported from the exporting step to the side of the frame production line. Meanwhile, a previously assembled aluminum frame is loaded to the frame production line.
- the aluminum frame comprises projections for supporting the opposite surface of the light-receiving surface of the solar cell module on which the solar cell has been arranged.
- the aluminum frame is shaped such that it can be arranged over the entire periphery of the solar cell module and has a structure in which the light-receiving surface side of the solar cell module is in an open condition.
- the solar cell panel was treated for 3,000 hours at a temperature of 85°C and a relative humidity of 85% RH, and the appearance of the back surface and the reduction in output power (JIS-C8913 (1998)) were evaluated as follows.
- a polyester chip ⁇ -1 was produced by the following method.
- the temperature of the reaction system was slowly increased from 230°C to 290°C and the pressure was reduced to 0.1 kPa.
- the time for reaching the final temperature of 290°C and the time for reaching the final pressure of 0.1 kPa were both set at 60 minutes.
- the reaction system was allowed to react for 2 hours (3 hours after the start of polymerization). Thereafter, the pressure of the reaction system was restored to normal pressure by purging with nitrogen so as to terminate the polymerization reaction and the reaction product was extruded into cold water in the form of a strand and immediately cut, thereby obtaining a polyester chip ⁇ .
- polyester chip ⁇ had a grass transition temperature of 80°C, a cold crystallization temperature of 157°C, a melting point of 255°C, an intrinsic viscosity of 0.52 and an amount of terminal carboxyl groups of 15.0 eq/ton.
- polyester chip ⁇ was dried and crystallized at 160°C for 6 hours under vacuum. Then, the resulting polyester chip ⁇ was subjected to solid phase polymerization at 220°C for 8 hours under vacuum to obtain a polyester chip ⁇ -1.
- the thus obtained polyester chip ⁇ -1 had a grass transition temperature of 82°C, a cold crystallization temperature of 165°C, a melting point of 255°C, an intrinsic viscosity of 0.85 and an amount of terminal carboxyl groups of 10 eq/ton.
- the polyester chip ⁇ -1 and silica having the particle size shown in Table 1 were mixed and the resulting mixture was melt-kneaded to prepare a master pellet.
- the thus obtained master pellet had a silica concentration of 10% by mass.
- this master pellet was mixed with the polyester chip ⁇ -1, and the resulting mixture was dried under reduced pressure at 180°C for 3 hours, fed to an extruder E heated to 280°C and introduced to a T-die mouthpiece.
- the mixture of the master pellet and polyester chip ⁇ -1 was mixed and introduced such that the silica concentration became as shown in Table 1.
- the molten mixture of the polyester chip ⁇ -1 and masterbatch was extruded from the T-die mouthpiece in the form of a sheet to obtain a molten monolayer sheet, and this molten monolayer sheet was cooled and solidified in contact with a casting drum having a surface temperature of 25°C while applying thereto a static charge, thereby preparing an unstretched film.
- the thus obtained unstretched film was preheated with a group of heated rolls and then stretched in the machine direction at a temperature of 90°C and a draw ratio of 3.5 times using a silicon stretching roll (surface hardness: 40°) and a silicon nip roll (surface roughness: 40°) with a nip pressure of 0.1 MPa.
- the resulting film was cooled with a group of rolls having a temperature of 25°C to obtain a uniaxially stretched film.
- the thus obtained uniaxially stretched film was introduced to a 80°C preheating zone (nozzle air flow rate: 3 m/s, nozzle-film distance: 120 mm) in a tenter with both ends of the film being held with clips, and then continuously stretched in the width direction (TD direction) perpendicular to the machine direction at a draw ratio of 3.7 times in a 90°C heating zone. Further, in a heat treatment zone of the tenter, the resulting film was heat-treated at a temperature of 210°C for 10 seconds and then relaxed by 4% in the width direction at a temperature of 210°C.
- the respective polyester films were obtained in the same manner as in Example 1 except that the compositions thereof were changed as shown in Tables 1-1, 1-2, 1-3 and 2.
- the properties of the thus obtained polyester films and the like are shown in Tables 1-1, 1-2, 1-3 and 2. It is noted here that, as raw materials, masterbatches in which the type and concentration of the additive were changed were used (the concentration values [% by mass] shown in Table 2 for Examples 29 to 40 each represent the concentration of a blended incompatible resin with respect to the total weight of a layer containing the incompatible resin (polyester + incompatible resin).
- the respective polyester films were obtained in the same manner as in Example 1, except that only the polyester chip ⁇ -1 obtained in Reference Example 1 was dried under reduced pressure at 180°C for 3 hours, fed to the extruder E heated to 280°C and then introduced to the T-die mouthpiece.
- the thus obtained polyester films were molded using an imprint apparatus equipped with a die such that the resultants had the respective surface profiles shown in Tables 1-1, 1-2 and 1-3.
- the properties of the thus obtained polyester films and the like are shown in Tables 1-1, 1-2 and 1-3.
- polyester films were obtained in the same manner as in Example 5 except that the conditions for forming each polyester film were changed as shown in Table 3.
- the properties of the thus obtained polyester films and the like are shown in Table 3.
- polyester films were obtained in the same manner as in Example 14 except that the conditions for forming each polyester film were changed as shown in Table 3.
- the properties of the thus obtained polyester films and the like are shown in Table 3.
- the polyester chip ⁇ -1 and silica having the particle size shown in Table 4 were mixed and the resulting mixture was melt-kneaded to prepare a master pellet.
- the thus obtained master pellet had a silica concentration of 10% by mass.
- this master pellet was mixed with the polyester chip ⁇ -1, and the resulting mixture was dried under reduced pressure at 180°C for 3 hours, fed to the extruder E heated to 280°C and introduced to the T-die mouthpiece.
- the mixture of the master pellet and polyester chip ⁇ -1 was mixed and introduced such that the silica concentration became as shown in Table 1.
- the resulting polyester chip ⁇ -1 was fed to an extruder F heated to 280°C and introduced to a T-die mouthpiece.
- the molten materials fed to the extruder E and the materials fed to the extruder F were merged in a T-die mouthpiece to be laminated with each other and the resultant was extruded from the T-die mouthpiece in the form of a sheet to obtain a molten laminated sheet.
- This molten laminated sheet was then cooled and solidified in contact with a casting drum having a surface temperature of 25°C while applying thereto a static charge, thereby preparing an unstretched film (laminated film).
- the lamination ratio of the thus obtained unstretched film, layer A (a layer constituted by the materials fed to the extruder E)/layer B (a layer constituted by the materials fed to the extruder F) was 1/4.
- polyester films were obtained in the same manner as in Example 58 except that the compositions thereof were changed as shown in Tables 4-1 and 4-2.
- the properties of the thus obtained polyester films and the like are shown in Tables 4-1 and 4-2. It is noted here, however, that the polyester chip ⁇ -1 and masterbatches in which the additive was changed were used as raw materials.
- polyester films were obtained in the same manner as in Example 5 except that the conditions for forming each polyester film were changed as shown in Table 5.
- the properties of the thus obtained polyester films and the like are shown in Table 5.
- polyester films were obtained in the same manner as in Example 14 except that the conditions for forming each polyester film were changed as shown in Table 5.
- the properties of the thus obtained polyester films and the like are shown in Table 5.
- polyester films were obtained in the same manner as in Example 1 except that the compositions thereof were changed as shown in Table 6.
- the properties of the thus obtained polyester films and the like are shown in Table 6. It is noted here, however, that the polyester chip ⁇ -1 and masterbatches in which the additive was changed were used as raw materials.
- COOH amount of terminal carboxyl groups
- PCHT cyclohexadimethyl ether
- ABS acryl butadiene styrene resin
- PC polycarbonate resin
- PEI polyetherimide resin
- PET polyethylene terephthalate
- BaSO 4 barium sulfate
- Ca carbonate calcium carbonate
- a polyester film having excellent wet heat resistance can be provided.
- the polyester film by taking advantage of its characteristic features, can be suitably used as a film for a solar cell backsheet.
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EP2476552A4 (fr) * | 2009-09-11 | 2013-04-10 | Toray Industries | Film polyester, plaque arriere de cellule solaire comprenant ledit film et cellule solaire comprenant ladite plaque |
CN102575090B (zh) | 2009-10-27 | 2013-12-11 | 东丽株式会社 | 聚对苯二甲酸乙二醇酯组合物、其制造方法及聚对苯二甲酸乙二醇酯膜 |
JP5553619B2 (ja) * | 2010-01-15 | 2014-07-16 | 三菱樹脂株式会社 | 太陽電池裏面封止用二軸配向ポリエステルフィルム |
JP5901046B2 (ja) * | 2010-02-19 | 2016-04-06 | 国立大学法人 千葉大学 | OATP1B3mRNAの新規な選択的スプライシングバリアント |
JP2011178866A (ja) * | 2010-02-26 | 2011-09-15 | Fujifilm Corp | ポリエステルフィルム及びその製造方法、並びに太陽電池裏面封止用ポリエステルフィルム、太陽電池裏面保護膜及び太陽電池モジュール |
JP5283648B2 (ja) * | 2010-03-04 | 2013-09-04 | 富士フイルム株式会社 | ポリエステルフィルム及びその製造方法、並びに太陽電池モジュール |
US8893475B2 (en) * | 2010-03-11 | 2014-11-25 | Cummins Inc. | Control system for doser compensation in an SCR system |
JP5477114B2 (ja) | 2010-03-31 | 2014-04-23 | 東レ株式会社 | 蒸着用二軸配向ポリエステルフィルムおよびガスバリアフィルム |
JP5404521B2 (ja) * | 2010-04-29 | 2014-02-05 | 三菱樹脂株式会社 | 深絞り成形同時転写用二軸延伸ポリエステルフィルム |
JP5604994B2 (ja) * | 2010-06-04 | 2014-10-15 | 東洋紡株式会社 | レンズシート用ベースフィルム |
WO2011156571A1 (fr) * | 2010-06-09 | 2011-12-15 | Toray Plastics (America), Inc. Lumirror Division | Film de polyester optiquement transparent et résistant aux uv et à l'hydrolyse |
-
2012
- 2012-11-19 JP JP2013506035A patent/JP5331266B1/ja active Active
- 2012-11-19 WO PCT/JP2012/079972 patent/WO2013080827A1/fr active Application Filing
- 2012-11-19 CN CN201280058014.8A patent/CN103946285B/zh active Active
- 2012-11-19 US US14/360,484 patent/US9530917B2/en active Active
- 2012-11-19 EP EP12852635.7A patent/EP2787027A4/fr not_active Withdrawn
- 2012-11-19 IN IN4731CHN2014 patent/IN2014CN04731A/en unknown
- 2012-11-19 KR KR1020147013773A patent/KR102017514B1/ko active IP Right Grant
- 2012-11-19 MY MYPI2014701344A patent/MY172054A/en unknown
- 2012-11-19 SG SG11201402189RA patent/SG11201402189RA/en unknown
- 2012-11-28 TW TW101144458A patent/TWI614291B/zh not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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KR20140098088A (ko) | 2014-08-07 |
SG11201402189RA (en) | 2014-09-26 |
JP5331266B1 (ja) | 2013-10-30 |
CN103946285B (zh) | 2016-07-06 |
CN103946285A (zh) | 2014-07-23 |
US9530917B2 (en) | 2016-12-27 |
TW201331277A (zh) | 2013-08-01 |
EP2787027A4 (fr) | 2015-07-22 |
MY172054A (en) | 2019-11-13 |
US20140352776A1 (en) | 2014-12-04 |
TWI614291B (zh) | 2018-02-11 |
JP6036589B2 (ja) | 2016-11-30 |
KR102017514B1 (ko) | 2019-09-03 |
IN2014CN04731A (fr) | 2015-09-18 |
JPWO2013080827A1 (ja) | 2015-04-27 |
WO2013080827A1 (fr) | 2013-06-06 |
JP2013231197A (ja) | 2013-11-14 |
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